Triorganosilylphenoxysilanes



Patented Sept. 23, 1 9 5 2 UNITED STATES PATENT OFF-ICETRIORGANOSiLYLPHENOXYSILANES 3011111 14. cier, ;n.,'{i 1ttsbur h, Pa.,assignor to new Corning Corporation, Midland, Mich., a ooffioiat'ibn 62Michigan I No Drawing. Appucau ajsf r'tei itgr it"ii, Serial No.185,516. In Great Britain Novem= bar -29. 1949 r 1 (c1. see-an st 1 l 12 r I This invention relates to tfioifiiiosilylpli-"wh'ehthe'illtviiig'classesoiiphenoxysilanesand ysilanes. 7 smart oralksxysi-iafies are reacted:

In the applicafit"s copend nig appl cation ri ed 7 concurrentlyherewith, the trialliylsilylphfioxy- R silanes were disclosed andclaimed. "Tfi'isfiiiv'en- 5 a tion relates to similar compounds in whichone i J or more of the silicon atoms has an alkoxy group w th g g tm'Rgs'iR-SCI "ifid j attached thereto. I

The compounds of this invention are useful as intermediates in thepreparation of organosilyl- 10 phenols and may be employed as exchangemedia and thermo expansion fluids.

This invention relates to compounds of the with R2Si(0R)Cl or R'a'SiGl.In these formulae type R represents an alkyl radical.

c I5 The reaction of halophenoxys lanes; chlorosilanes or alkoxysilanesand an alkaliymeta-iis a insi 0G I complex phenomena. Not only are thenormal reaction products which would be expectedfrem asample-condensation 'reactionproduced; but also in which R is analkylradical such as- ,methyl, 20 s f t 9 z 1 propyl and octadecyloralkoxy radical; there The rearrangement products which voccur being atleast 2 alkyl radicals attached to each silicon atom anad an al-koxyradical attached to at least one of the silicon atoms, R is alkyl suchas, for example, methyl, amyl, octadecyl and cyclohexyl, orv phenyl andc has a value from 0 to 1.

The above compounds are prepared by reacting a halophenoxysilane oithetype a silane of the type RiasiYt wafid an lk-all metal. In thesilane R is an alkyl radicalsuch ethyl and octadecyl, Y is a imagealkoxy radical there being les'' th gen atoms per silicon atom, and d T2 to 3. In the phenoxysilane X ahalhgn atom and R is an alkyloralkoit'y' radical.

The method for carrying out the process is that of adding a mixture ofthe reactants to a molten alkali metal; Preferably the alkali metal issodium or potassium.

If desired, an inert solvent, boiling above the melting. point oi thealkali metal may be employed. Such solvents include,-toreai'amplet'benzene, toluene, saturated aliphatic hydrocarbons boilingabove 65 C. and higher honing tliers. In carrying out therea-ction, careshould betakn that the reaction medium is essentially of active hydrogencompounds such as mccncismater and acids.

The products or invention attained 5 when the above reactions arecarriedoutin the presence of an alkali metal are illustrated by thefollowing example. When a compound of the type mtnoisro is condensedwith a compound of the type R2Si617l one would normally eiipect that thepredominant product would becompounds of the following type are alsoob-Rune- 510 1 taining the following units:

sodium in boiling toluene.

The halophenoxysilanes employed in this invention may be prepared bycondensing halophenols of the type alkyl or alkoxy there being at leasttwo alkyls per silicon and Y is chlorine. or alkoxy. m-The products areproduced by mixing the phenol'and silane whereupon condensation betweenthe phenolic hydroxyl and the silane Y group takes place with theelimination of I-ICl or an alcohol.

The reaction willproceed at room temperature KA a 106 g. ofp-chlorophenoxyethoxydimethylsil- 'ane' was 'mixed with 76 g. ofethoxydimethylchlorosilane and reacted with 23 'g. of molten The mixturewas filtered and distilled and there was obtained 45 g. of EtOMezSi (p-[EtOMezSil CsH40') boiling point 168 C. at 25 mm. Iii-addition therewasobtained-a nondistillable' material which was a complex mixture ofrearrangement productsxand polymeric materials having the followingstructural units? j ocemsiMeioo6His1Ma- EXAMPLE;Z;

A mixture of M8 g. of dimethyldiethoxysilane and 200.5 g. ofp-chlorophenoxytrimethylsilane was added to 50.6 g. of sodium in boilingtoluene.

} jsilylphenoxytrimethylsilane, with silanes of the type R."3SiY where Ris chlorosilane was added to react with this sodi-MesSi(p-EtOMezsicsI-liO and EtOMezSi(p-'VI83SiCeI-IsO'-), 152 C. at 25mm.,

boiling point 163 C. at 25 mm, together with the unexpectedrearrangement product Me3Si(p-Me3SiOCcI-I4O) boiling point 132 C. at 25min.

boiling point ,EXAMPLE 3 when a mixture of 214.5 g. of 3-methy1-4-chlorophenoxytrimethylsilane and 152 g. of eth- 'oxydimethylchlorosilaneis reacted with 50 g. of molten sodium. by the procedure of Example 1,

there is obtained 3-methyl-4=-ethoxydimethyl-.melsus-igre-i-(sconezsnc6mo-1 When sinners of 276.5 g. of 2-phenyl-4-chlorophenoxytrimethylsilane and 152 g. of ethoxydimethylchlorosilane isreacted with 50 g.

of molten sodium by the procedure of Example 1, there-is obtained as aproduct the compound Me3s1[2-c611- to eisi) CsHsO-J z -phenyl-'a-ethoxydimethylsilylphenoxysilane. That which is claimed is:

1. Compounds of the formula V I V aradical selected the group consistingofi'alkyl and alkoxy radicals, there being at least Zalkyl radicalsattached to each silicon atom and an alkoxy radical attached to at leastone of, the silicon atoms, R. is a radical selected from the groupconsisting of alkyl and phenyl radicals, and c is an integer from 0 to 1inclusive.

5. The method which comprises reacting a halophenoxysilane of theformula I i in which R is .a radical selected from the group consistingof alkyl and alkoxy radicals at least two of the radicals being alkyl,R, is a radical selected from the {group consisting of alkyl and phenylradicals, c is an integer from 0 to 1 inclusive, and X is a halogenatom, with an alkylsilane of the formula RaSiY4 a, in which R is analkyl radical, Y is a substituentselected from the group consisting ofhalogen atoms and alkoxyradicals there being less than -2 halogen atomsper silicon atom, and a is an integer from 2 to 3 inclusive, bycontacting the two with an alkali metal whereby acompound of the formulaisformed. l p

6. Themethod in accord with claim 5 wherein the halophenoxy" silane ischlorophenoxyethoxydimethylsilane.

7'.1-Themethodiin accord withclaim 5 wherein the halop'henoxysilane .ischlorophenoxytrimethylsilane. 1 f

8. The method in accord with claim 5 where'- in the alkylsilane isdimethyldiethoxysilane.

9. The method in accord with claim 5 wherein the alkylsilane isethoxydimethylchlorosilane.

10. The method which comprises reacting a halophenoxysilane of theformula in which R is a radical selected from the group consisting ofalkyl and alkoxy radicals at least two of the radicals being alkyl, R isa radical selected from the group consisting of alkyl and phenylradicals, c is an integer from 0 to 1 inclusive, and X is a halogenatom, with an alkylsilane of the formula RaSiY4 a, in which R is analkyl radical, Y is a substituent selected from the group consisting ofhalogen atoms and alkoxy radicals, there being less than two halogenatoms per silicon atom, and a is an integer from 2 to 3 inclusive, bycontacting the two in liquid phase with a molten alkali metal, whereisformed.

11'. The method in accordance with claim 10 wherein thehalophenoxysilane is chlorophenoxyethoxydimethylsilane.

12. The method in accordance with claim 10 wherein the halophenoxysilaneis chlorophenoxytrimethylsilane.

13. The method in accordance with claim 10 wherein the alkylsilane isdimethyldiethoxysilane.

14. The method in accordance with claim 10 wherein the alkylsilane isethoxydimethylchlorosilane.

JOHN L. SPEIER, J R.

No references cited.

1. COMPOUNDS OF THE FORMULA